US20240105997A1 - Electrolytic solution for secondary battery, and secondary battery - Google Patents

Electrolytic solution for secondary battery, and secondary battery Download PDF

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US20240105997A1
US20240105997A1 US18/510,854 US202318510854A US2024105997A1 US 20240105997 A1 US20240105997 A1 US 20240105997A1 US 202318510854 A US202318510854 A US 202318510854A US 2024105997 A1 US2024105997 A1 US 2024105997A1
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lithium
electrolytic solution
secondary battery
formula
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Masayuki Ihara
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Murata Manufacturing Co Ltd
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Murata Manufacturing Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present technology relates to an electrolytic solution for a secondary battery, and a secondary battery.
  • the secondary battery includes a positive electrode, a negative electrode, and an electrolytic solution (an electrolytic solution for a secondary battery).
  • a configuration of the secondary battery has been considered in various ways.
  • an electrolytic solution includes an imide compound represented by R F 1 —S( ⁇ O) 2 —NH—S( ⁇ O) 2 —NH—S( ⁇ O) 2 —R F 2 .
  • an electrolyte salt included in an electrolytic solution includes an imide anion represented by F—S( ⁇ O ) 2 —N ⁇ —C( ⁇ O)—N ⁇ —S( ⁇ O) 2 —F or F—S( ⁇ O) 2 —N ⁇ —S( ⁇ O) 2 —C 6 H 4 —S( ⁇ O) 2 —N ⁇ —S( ⁇ O) 2 —F.
  • the present technology relates to an electrolytic solution for a secondary battery, and a secondary battery.
  • An electrolytic solution for a secondary battery includes an electrolyte salt and a lithium fluorophosphate.
  • the electrolyte salt includes an imide anion, and the imide anion includes at least one of an anion represented by Formula (1), an anion represented by Formula (2), an anion represented by Formula (3), or an anion represented by Formula (4).
  • the lithium fluorophosphate includes lithium monofluorophosphate (Li 2 PFO 3 ), lithium difluorophosphate (LiPF 2 O 2 ), or both.
  • a secondary battery according to an embodiment of the present technology includes a positive electrode, a negative electrode, and an electrolytic solution.
  • the electrolytic solution has a configuration similar to the configuration of the electrolytic solution for a secondary battery according to an embodiment of the present technology described herein.
  • the electrolytic solution for a secondary battery includes the electrolyte salt and the lithium fluorophosphate.
  • the electrolyte salt includes, as the imide anion, at least one of the anion represented by Formula (1), the anion represented by Formula (2), the anion represented by Formula (3), or the anion represented by Formula (4).
  • the lithium fluorophosphate includes lithium monofluorophosphate, lithium difluorophosphate, or both. Accordingly, it is possible to achieve a superior battery characteristic.
  • effects of the present technology are not necessarily limited to those described herein and may include any of a series of suitable effects in relation to the present technology.
  • FIG. 1 is a perspective view of a configuration of a secondary battery according to an embodiment of the present technology.
  • FIG. 2 is a sectional view of a configuration of a battery device illustrated in FIG. 1 .
  • FIG. 3 is a block diagram illustrating a configuration of an application example of the secondary battery.
  • electrolytic solution for a secondary battery (hereinafter simply referred to as an “electrolytic solution”) according to an embodiment of the present technology.
  • the electrolytic solution to be described here is to be used in a secondary battery, which is an electrochemical device.
  • the electrolytic solution may be used in other electrochemical devices.
  • Other electrochemical devices are not particularly limited in kind, and specific examples thereof include a capacitor.
  • the electrolytic solution is a liquid electrolyte.
  • the electrolytic solution includes an electrolyte salt and a lithium fluorophosphate. More specifically, the electrolytic solution includes an electrolyte salt, a lithium fluorophosphate, and a solvent in which the electrolyte salt and the lithium fluorophosphate are each dispersed or dissolved. Note that the lithium fluorophosphate is excluded from the electrolyte salt.
  • the electrolyte salt is a compound to be ionized in a solvent, and includes an anion and a cation. Note that only one electrolyte salt may be used, or two or more electrolyte salts may be used.
  • the anion includes an imide anion.
  • the imide anion includes one or more of an anion represented by Formula (1), an anion represented by Formula (2), an anion represented by Formula (3), or an anion represented by Formula (4).
  • the electrolyte salt includes the imide anion as the anion.
  • the anion represented by Formula (1) is referred to as a “first imide anion”
  • the anion represented by Formula (2) is referred to as a “second imide anion”
  • the anion represented by Formula (3) is referred to as a “third imide anion”
  • the anion represented by Formula (4) is referred to as a “fourth imide anion”.
  • first imide anion may be used, or two or more first imide anions may be used.
  • second imide anion may be used, or two or more second imide anions may be used.
  • third imide anion may be used, or two or more third imide anions may be used.
  • fourth imide anion may be used, or two or more fourth imide anions may be used.
  • a reason why the anion includes the imide anion is as described below.
  • a first reason is that upon charging and discharging of a secondary battery using the electrolytic solution, a high-quality film derived from the electrolyte salt is formed on a surface of each of a positive electrode and a negative electrode. As a result, a reaction of the electrolytic solution (specifically the solvent) with each of the positive electrode and the negative electrode is suppressed, which suppresses decomposition of the electrolytic solution.
  • a second reason is that the above-described film is used to improve a migration velocity of the cation near the surface of each of the positive electrode and the negative electrode.
  • a third reason is that the migration velocity of the cation is improved also in the electrolytic solution.
  • the first imide anion is a chain anion (a divalent negative ion) including two nitrogen atoms (N) and three functional groups (W1 to W3) as represented by Formula (1).
  • Each of R1 and R2 is not particularly limited as long as each of R1 and R2 is one of a fluorine group (—F) or a fluorinated alkyl group.
  • R1 and R2 may be groups that are identical to each other, or may be groups that are different from each other. Accordingly, each of R1 and R2 is not a group such as a hydrogen group (—H) or an alkyl group.
  • the fluorinated alkyl group is a group resulting from substituting one or more hydrogen groups (—H) of an alkyl group with one or more fluorine groups. Note that the fluorinated alkyl group may have a straight-chain structure; or a branched structure having one or more side chains.
  • carbon number of the fluorinated alkyl group is specifically within a range from 1 to 10 both inclusive. A reason for this is that solubility and ionizability of the electrolyte salt including the first imide anion improve.
  • fluorinated alkyl group examples include a perfluoromethyl group (—CF 3 ) and a perfluoroethyl group (—C 2 F 5 ).
  • Each of W1 to W3 is not particularly limited as long as each of W1 to W3 is one of a carbonyl group, a sulfinyl group, or a sulfonyl group.
  • W1 to W3 may be groups that are identical to each other, or may be groups that are different from each other. It goes without saying that only any two of W1 to W3 may be groups that are identical to each other.
  • the second imide anion is a chain anion (a trivalent negative ion) including three nitrogen atoms and four functional groups (X1 to X4) as represented by Formula (2).
  • Each of X1 to X4 is not particularly limited as long as each of X1 to X4 is one of a carbonyl group, a sulfinyl group, or a sulfonyl group.
  • X1 to X4 may be groups that are identical to each other, or may be groups that are different from each other. It goes without saying that only any two of X1 to X4 may be groups that are identical to each other, or only any three of X1 to X4 may be groups that are identical to each other.
  • the third imide anion is a cyclic anion (a divalent negative ion) including two nitrogen atoms, three functional groups (Y1 to Y3), and one linking group (R5) as represented by Formula (3).
  • the fluorinated alkylene group that is R5 is a group resulting from substituting one or more hydrogen groups of an alkylene group with one or more fluorine groups. Note that the fluorinated alkylene group may have a straight-chain structure; or a branched structure having one or more side chains.
  • carbon number of the fluorinated alkylene group is specifically within a range from 1 to 10 both inclusive. A reason for this is that solubility and ionizability of the electrolyte salt including the third imide anion improve.
  • fluorinated alkylene group examples include a perfluoromethylene group (—CF 2 —) and a perfluoroethylene group (—C 2 F 4 —).
  • Each of Y1 to Y3 is not particularly limited as long as each of Y1 to Y3 is one of a carbonyl group, a sulfinyl group, or a sulfonyl group.
  • Y1 to Y3 may be groups that are identical to each other, or may be groups that are different from each other. It goes without saying that only any two of Y1 to Y3 may be groups that are identical to each other.
  • the fourth imide anion is a chain anion (a divalent negative ion) including two nitrogen atoms (N), four functional groups (Z1 to Z4), and one linking group (R8) as represented by Formula (4).
  • R8 is not particularly limited as long as R8 is one of an alkylene group, a phenylene group, a fluorinated alkylene group, or a fluorinated phenylene group.
  • the alkylene group may have a straight-chain structure; or a branched structure having one or more side chains. Although not particularly limited, carbon number of the alkylene group is specifically within a range from 1 to 10 both inclusive. A reason for this is that solubility and ionizability of the electrolyte salt including the fourth imide anion improve.
  • Specific examples of the alkylene group include a methylene group (—CH 2 —), an ethylene group (—C 2 H 4 —), and a propylene group (—C 3 H 6 —).
  • the fluorinated phenylene group is a group resulting from substituting one or more hydrogen groups of a phenylene group with one or more fluorine groups.
  • Specific examples of the fluorinated phenylene group include a monofluorophenylene group (—C 6 H 3 F—).
  • Each of Z1 to Z4 is not particularly limited as long as each of Z1 to Z4 is one of a carbonyl group, a sulfinyl group, or a sulfonyl group.
  • Z1 to Z4 may be groups that are identical to each other, or may be groups that are different from each other. It goes without saying that only any two of Z1 to Z4 may be groups that are identical to each other, or only any three of Z1 to Z4 may be groups that are identical to each other.
  • first imide anion examples include respective anions represented by Formulae (1-1) to (1-30).
  • Specific examples of the second imide anion include respective anions represented by Formulae (2-1) to (2-22).
  • third imide anion examples include respective anions represented by Formulae (3-1) to (3-15).
  • fourth imide anion examples include respective anions represented by Formulae (4-1) to (4-65).
  • the cation is not particularly limited in kind. Specifically, the cation includes one or more of light metal ions. In other words, the electrolyte salt includes a light metal ion as the cation. A reason for this is that a high voltage is obtainable.
  • the light metal ion is not particularly limited in kind, and specific examples thereof include an alkali metal ion and an alkaline earth metal ion.
  • Specific examples of the alkali metal ion include a sodium ion and a potassium ion.
  • Specific examples of the alkaline earth metal ion include a beryllium ion, a magnesium ion, and a calcium ion.
  • the light metal ion may be another light metal ion such as an aluminum ion.
  • the light metal ion preferably includes a lithium ion.
  • a reason for this is that a sufficiently high voltage is obtainable.
  • a content of the electrolyte salt in the electrolytic solution is not particularly limited, and may be set as desired.
  • the content of the electrolyte salt is preferably within a range from 0.2 mol/kg to 2 mol/kg both inclusive. A reason for this is that high ion conductivity is obtainable.
  • the “content of the electrolyte salt” described here is a content of the electrolyte salt with respect to the solvent.
  • a secondary battery is disassembled to collect the electrolytic solution, following which the electrolytic solution is analyzed by inductively coupled plasma (ICP) optical emission spectroscopy.
  • ICP inductively coupled plasma
  • the procedure of identifying the content described here is similarly applicable to that in a case of identifying a content of each of components of the electrolytic solution other than the electrolyte salt to be described below.
  • the “components of the electrolytic solution other than the electrolyte salt” include, for example, the lithium fluorophosphate, any other electrolyte salt, and an additive.
  • the lithium fluorophosphate is a compound including lithium (Li), phosphorous (P), fluorine (F), and oxygen (O) as constituent elements (a lithium salt having a specific configuration). More specifically, the lithium fluorophosphate includes lithium monofluorophosphate, lithium difluorophosphate, or both.
  • a reason why the electrolytic solution includes the lithium fluorophosphate is that a decomposition reaction of the electrolytic solution is suppressed while securing ion conductivity. In this case, in particular, the decomposition reaction of the electrolytic solution is effectively suppressed even when the secondary battery using the electrolytic solution is used (charged and discharged) and stored in a high-temperature environment.
  • a content of the lithium fluorophosphate in the electrolytic solution is not particularly limited and may be set as desired.
  • the content of the lithium fluorophosphate is preferably within a range from 0.05 wt % to 3 wt % both inclusive. A reason for this is that the decomposition reaction of the electrolytic solution is suppressed while securing ion conductivity.
  • the solvent includes one or more of non-aqueous solvents (organic solvents), and the electrolytic solution including the non-aqueous solvent(s) is a so-called non-aqueous electrolytic solution.
  • the non-aqueous solvent is, for example, an ester or an ether, more specifically, a carbonic-acid-ester-based compound, a carboxylic-acid-ester-based compound, or a lactone-based compound, for example.
  • the carbonic-acid-ester-based compound is, for example, a cyclic carbonic acid ester or a chain carbonic acid ester.
  • a cyclic carbonic acid ester include ethylene carbonate and propylene carbonate.
  • a chain carbonic acid ester include dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.
  • the carboxylic-acid-ester-based compound is, for example, a chain carboxylic acid ester.
  • chain carboxylic acid ester include methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, ethyl trimethylacetate, methyl butyrate, and ethyl butyrate.
  • the lactone-based compound is, for example, a lactone.
  • Specific examples of the lactone include ⁇ -butyrolactone and ⁇ -valerolactone.
  • the ether may be, for example, 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxolane, or 1,4-dioxane.
  • the electrolytic solution may further include one or more of other electrolyte salts.
  • a reason for this is that the migration velocity of the cation near the surface of each of the positive electrode and the negative electrode is further improved, and the migration velocity of the cation is further improved also in the electrolytic solution.
  • a content of the other electrolyte salt(s) in the electrolytic solution is not particularly limited, and may be set as desired.
  • the other electrolyte salts are not particularly limited in kind, and specific examples thereof include a light metal salt such as a lithium salt. Note that the electrolyte salt described above is excluded from the lithium salt described here.
  • lithium salt examples include lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(fluorosulfonyl)imide (LiN(FSO 2 ) 2 ), lithium bis(trifluoromethanesulfonyl)imide (LiN(CF 3 SO 2 ) 2 ), lithium tris(trifluoromethanesulfonyl)methide (LiC(CF 3 SO 2 ) 3 ), lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 ), lithium difluorooxalatoborate (LiBF 2 (C 2 O 4 )), lithium difluorodi(oxalato)borate (LiPF 2 (C 2 O 4 ) 2 ), and lithium tetrafluorooxalatophosphate (LiPF 4 ),
  • the other electrolyte salts preferably include one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(fluorosulfonyl)imide, and lithium bis(oxalato)borate.
  • a reason for this is that the migration velocity of the cation near the surface of each of the positive electrode and the negative electrode is sufficiently improved, and the migration velocity of the cation is sufficiently improved also in the electrolytic solution.
  • the electrolytic solution may further include one or more of additives.
  • a reason for this is that upon charging and discharging of the secondary battery using the electrolytic solution, a film derived from the additive is formed on the surface of each of the positive electrode and the negative electrode, and the decomposition reaction of the electrolytic solution is therefore suppressed.
  • a content of the additive in the electrolytic solution is not particularly limited, and may be set as desired.
  • the additive is not particularly limited in kind, and specific examples thereof include an unsaturated cyclic carbonic acid ester, a fluorinated cyclic carbonic acid ester, a sulfonic acid ester, a dicarboxylic acid anhydride, a disulfonic acid anhydride, a sulfuric acid ester, a nitrile compound, and an isocyanate compound.
  • the unsaturated cyclic carbonic acid ester is a cyclic carbonic acid ester having an unsaturated carbon bond (a carbon-carbon double bond).
  • the number of unsaturated carbon bonds is not particularly limited, and may be only one, or two or more.
  • Specific examples of the unsaturated cyclic carbonic acid ester include vinylene carbonate, vinylethylene carbonate, and methylene ethylene carbonate.
  • the fluorinated cyclic carbonic acid ester is a cyclic carbonic acid ester including fluorine as a constituent element. That is, the fluorinated cyclic carbonic acid ester is a compound resulting from substituting one or more hydrogen groups of a cyclic carbonic acid ester with one or more fluorine groups. Specific examples of the fluorinated cyclic carbonic acid ester include monofluoroethylene carbonate and difluoroethylene carbonate.
  • the sulfonic acid ester is, for example, a cyclic monosulfonic acid ester, a cyclic disulfonic acid ester, a chain monosulfonic acid ester, or a chain disulfonic acid ester.
  • a cyclic monosulfonic acid ester include 1,3-propane sultone, 1-propene-1,3-sultone, 1,4-butane sultone, 2,4-butane sultone, and methanesulfonic acid propargyl ester.
  • Specific examples of the cyclic disulfonic acid ester include cyclodisone.
  • dicarboxylic acid anhydride examples include succinic anhydride, glutaric anhydride, and maleic anhydride.
  • disulfonic acid anhydride examples include ethanedisulfonic anhydride and propanedisulfonic anhydride.
  • sulfuric acid ester examples include ethylene sulfate(1,3,2-dioxathiolan 2,2-dioixide).
  • the nitrile compound is a compound having one or more cyano groups (—CN).
  • Specific examples of the nitrile compound include octanenitrile, benzonitrile, phthalonitrile, succinonitrile, glutaronitrile, adiponitrile, cebaconitrile, 1,3,6-hexanetricarbonitrile, 3,3′-oxydipropionitrile, 3-butoxypropionitrile, ethylene glycol bispropionitrile ether, 1,2,2,3-tetracyanopropane, tetracyanopropane, fumaronitrile, 7,7,8,8-tetracyanoquinodimethane, cyclopentanecarbonitrile, 1,3,5-cyclohexanetricarbonitrile, and 1,3-bis(dicyanomethylidene)indane.
  • the isocyanate compound is a compound including one or more isocyanate groups (—NCO). Specific examples of the isocyanate compound include hexamethylene diisocyanate.
  • the electrolyte salt is put into the solvent to thereby stir the solvent, following which the lithium fluorophosphate is added to the solvent to thereby stir the solvent.
  • the other electrolyte salt may be further added to the solvent, and the additive may be further added to the solvent.
  • the electrolyte salt and the lithium fluorophosphate are thereby each dispersed or dissolved in the solvent. As a result, the electrolytic solution is prepared.
  • the electrolytic solution includes the electrolyte salt and the lithium fluorophosphate.
  • the electrolyte salt includes one or more of the respective anions represented by Formulae (1) to (4) as the imide anion, and the lithium fluorophosphate includes lithium monofluorophosphate, lithium difluorophosphate, or both.
  • the decomposition reaction of the electrolytic solution is suppressed while securing ion conductivity.
  • the decomposition reaction of the electrolytic solution is effectively suppressed even in a high-temperature environment.
  • the electrolyte salt may include the light metal ion as the cation.
  • the light metal ion may include a lithium ion, which makes it possible to obtain a higher voltage. Accordingly, it is possible to achieve further higher effects.
  • the content of the electrolyte salt in the electrolytic solution may be within the range from 0.2 mol/kg to 2 mol/kg both inclusive. This makes it possible to obtain high ion conductivity. Accordingly, it is possible to achieve higher effects.
  • the content of the lithium fluorophosphate in the electrolytic solution may be within the range from 0.05 wt % to 3 wt % both inclusive. This sufficiently suppresses the decomposition reaction of the electrolytic solution. Accordingly, it is possible to achieve higher effects.
  • the electrolytic solution may further include, as one or more additives, one or more of the unsaturated cyclic carbonic acid ester, the fluorinated cyclic carbonic acid ester, the sulfonic acid ester, the dicarboxylic acid anhydride, the disulfonic acid anhydride, the sulfuric acid ester, the nitrile compound, and the isocyanate compound.
  • This suppresses the decomposition reaction of the electrolytic solution. Accordingly, it is possible to achieve higher effects.
  • the electrolytic solution may further include, as one or more other electrolyte salts, one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium bis(fluorosulfonyl)imide, and lithium bis(oxalato)borate.
  • This further improves the migration velocity of the cation. Accordingly, it is possible to achieve higher effects.
  • the secondary battery to be described here is a secondary battery that obtains a battery capacity using insertion and extraction of an electrode reactant, and includes a positive electrode, a negative electrode, and an electrolytic solution.
  • a charge capacity of the negative electrode is greater than a discharge capacity of the positive electrode.
  • an electrochemical capacity per unit area of the negative electrode is set to be greater than an electrochemical capacity per unit area of the positive electrode. This is to prevent precipitation of the electrode reactant on a surface of the negative electrode during charging.
  • the electrode reactant is specifically a light metal such as an alkali metal or an alkaline earth metal.
  • the alkali metal include lithium, sodium, and potassium.
  • Specific examples of the alkaline earth metal include beryllium, magnesium, and calcium.
  • the kind of the electrode reactant may be another light metal such as aluminum.
  • lithium-ion secondary battery lithium-ion secondary battery
  • lithium-ion secondary battery lithium is inserted and extracted in an ionic state.
  • FIG. 1 illustrates a perspective configuration of the secondary battery.
  • FIG. 2 illustrates a sectional configuration of a battery device 20 illustrated in FIG. 1 . Note that FIG. 1 illustrates a state in which an outer package film 10 and the battery device 20 are separated from each other, and illustrates a section of the battery device 20 along an XZ plane by a dashed line. FIG. 2 illustrates only a portion of the battery device 20 .
  • the secondary battery includes the outer package film 10 , the battery device 20 , a positive electrode lead 31 , a negative electrode lead 32 , and sealing films 41 and 42 .
  • the secondary battery described here is a secondary battery of a laminated-film type in which the outer package film 10 having flexibility or softness is used.
  • the outer package film 10 is an outer package member that contains the battery device 20 .
  • the outer package film 10 has a pouch-shaped structure in which the battery device 20 is sealed in a state of being contained inside the outer package film 10 .
  • the outer package film 10 thus contains a positive electrode 21 , a negative electrode 22 , and an electrolytic solution that are to be described later.
  • the outer package film 10 is a single film-shaped member, and is folded toward a folding direction F.
  • the outer package film 10 has a depression part 10 U to place the battery device 20 therein.
  • the depression part 10 U is what is called a deep drawn part.
  • the outer package film 10 is a three-layered laminated film including a fusion-bonding layer, a metal layer, and a surface protective layer that are stacked in this order from an inner side.
  • the fusion-bonding layer includes a polymer compound such as polypropylene.
  • the metal layer includes a metal material such as aluminum.
  • the surface protective layer includes a polymer compound such as nylon.
  • outer package film 10 is not particularly limited in configuration or the number of layers, and may be single-layered or two-layered, or may include four or more layers.
  • the sealing film 41 is interposed between the outer package film 10 and the positive electrode lead 31 .
  • the sealing film 42 is interposed between the outer package film 10 and the negative electrode lead 32 . Note that the sealing film 41 , the sealing film 42 , or both may be omitted.
  • the sealing film 41 is a sealing member that prevents entry, for example, of outside air into the outer package film 10 .
  • the sealing film 41 includes a polymer compound such as a polyolefin that has adherence to the positive electrode lead 31 .
  • Examples of the polyolefin include polypropylene.
  • a configuration of the sealing film 42 is similar to that of the sealing film 41 except that the sealing film 42 is a sealing member that has adherence to the negative electrode lead 32 . That is, the sealing film 42 includes a polymer compound such as a polyolefin that has adherence to the negative electrode lead 32 .
  • the battery device 20 is a power generation device that includes the positive electrode 21 , the negative electrode 22 , a separator 23 , and the electrolytic solution (not illustrated).
  • the battery device 20 is contained inside the outer package film 10 .
  • the battery device 20 is what is called a wound electrode body. That is, in the battery device 20 , the positive electrode 21 and the negative electrode 22 are stacked on each other with the separator 23 interposed therebetween, and the positive electrode 21 , the negative electrode 22 , and the separator 23 are wound about a winding axis P.
  • the winding axis P is a virtual axis extending in a Y-axis direction.
  • the positive electrode 21 and the negative electrode 22 are opposed to each other with the separator 23 interposed therebetween, and are wound.
  • a three-dimensional shape of the battery device 20 is not particularly limited.
  • the battery device 20 has an elongated three-dimensional shape.
  • a section of the battery device 20 intersecting the winding axis P that is, the section of the battery device 20 along the XZ plane, has an elongated shape defined by a major axis J 1 and a minor axis J 2 .
  • the major axis J 1 is a virtual axis that extends in an X-axis direction and has a larger length than the minor axis J 2 .
  • the minor axis J 2 is a virtual axis that extends in a Z-axis direction intersecting the X-axis direction and has a smaller length than the major axis J 1 .
  • the battery device 20 has an elongated cylindrical three-dimensional shape.
  • the section of the battery device 20 has an elongated, substantially elliptical shape.
  • the positive electrode 21 includes, as illustrated in FIG. 2 , a positive electrode current collector 21 A and a positive electrode active material layer 21 B.
  • the positive electrode current collector 21 A has two opposed surfaces on each of which the positive electrode active material layer 21 B is to be provided.
  • the positive electrode current collector 21 A includes an electrically conductive material such as a metal material. Specific examples of the metal material include aluminum.
  • the positive electrode active material layer 21 B includes one or more of positive electrode active materials into which lithium is insertable and from which lithium is extractable. Note that the positive electrode active material layer 21 B may further include one or more of other materials including, without limitation, a positive electrode binder and a positive electrode conductor.
  • the positive electrode active material layer 21 B is provided on each of the two opposed surfaces of the positive electrode current collector 21 A. Note that the positive electrode active material layer 21 B may be provided only on one of the two opposed surfaces of the positive electrode current collector 21 A on a side where the positive electrode 21 is opposed to the negative electrode 22 .
  • a method of forming the positive electrode active material layer 21 B is not particularly limited, and specifically includes one or more of methods including, without limitation, a coating method.
  • the positive electrode active material is not particularly limited in kind, and specific examples thereof include a lithium-containing compound.
  • the lithium-containing compound is a compound that includes lithium and one or more transition metal elements as constituent elements.
  • the lithium-containing compound may further include one or more other elements as one or more constituent elements.
  • the one or more other elements are not particularly limited in kind as long as the one or more other elements are each an element other than lithium and the transition metal elements.
  • the one or more other elements are any one or more of elements belonging to groups 2 to 15 in the long period periodic table.
  • the lithium-containing compound is not particularly limited in kind, and is specifically an oxide, a phosphoric acid compound, a silicic acid compound, or a boric acid compound, for example.
  • the oxide examples include LiNiO 2 , LiCoO 2 , LiCo 0.98 Al 0.01 Mg 0.01 O 2 , LiNi 0.05 Co 0.2 Mn 0.3 O 2 , LiNi 0.8 Co 0.15 Al 0.05 O 2 , LiNi 0.33 Co 0.33 Mn 0.33 O 2 , Li 1.2 Mn 0.52 Co 0.175 Ni 0.1 O 2 , Li 1.15 (Mn 0.65 Ni 0.22 Co 0.13 )O 2 , and LiMn 2 O 4 .
  • Specific examples of the phosphoric acid compound include LiFePO 4 , LiMnPO 4 , LiFe 0.5 Mn 0.5 PO 4 , and LiFe 0.3 Mn 0.7 PO 4 .
  • the positive electrode binder includes one or more of materials including, without limitation, a synthetic rubber and a polymer compound.
  • a synthetic rubber include a styrene-butadiene-based rubber, a fluorine-based rubber, and ethylene propylene diene.
  • the polymer compound include polyvinylidene difluoride, polyimide, and carboxymethyl cellulose.
  • the positive electrode conductor includes one or more of electrically conductive materials including, without limitation, a carbon material.
  • a carbon material include graphite, carbon black, acetylene black, and Ketjen black.
  • the electrically conductive material may be a metal material or a polymer compound, for example.
  • the negative electrode 22 includes, as illustrated in FIG. 2 , a negative electrode current collector 22 A and a negative electrode active material layer 22 B.
  • the negative electrode current collector 22 A has two opposed surfaces on each of which the negative electrode active material layer 22 B is to be provided.
  • the negative electrode current collector 22 A includes an electrically conductive material such as a metal material. Specific examples of the metal material include copper.
  • the negative electrode active material layer 22 B includes one or more of negative electrode active materials into which lithium is insertable and from which lithium is extractable. Note that the negative electrode active material layer 22 B may further include one or more of other materials including, without limitation, a negative electrode binder and a negative electrode conductor.
  • the negative electrode active material layer 22 B is provided on each of the two opposed surfaces of the negative electrode current collector 22 A.
  • the negative electrode active material layer 22 B may be provided only on one of the two opposed surfaces of the negative electrode current collector 22 A on a side where the negative electrode 22 is opposed to the positive electrode 21 .
  • a method of forming the negative electrode active material layer 22 B is not particularly limited, and specifically includes one or more of methods including, without limitation, a coating method, a vapor-phase method, a liquid-phase method, a thermal spraying method, and a firing (sintering) method.
  • the negative electrode active material is not particularly limited in kind, and specific examples thereof include a carbon material, a metal-based material, or both. A reason for this is that a high energy density is obtainable.
  • Specific examples of the carbon material include graphitizable carbon, non-graphitizable carbon, and graphite (natural graphite and artificial graphite).
  • the metal-based material is a material that includes, as one or more constituent elements, one or more elements among metal elements and metalloid elements that are each able to form an alloy with lithium. Specific examples of such metal elements and metalloid elements include silicon, tin, or both.
  • the metal-based material may be a simple substance, an alloy, a compound, a mixture of two or more thereof, or a material including two or more phases thereof. Specific examples of the metal-based material include TiSi 2 and SiO x (0 ⁇ x ⁇ 2 or 0.2 ⁇ x ⁇ 1.4).
  • the separator 23 is an insulating porous film interposed between the positive electrode 21 and the negative electrode 22 , and allows lithium ions to pass therethrough while preventing contact (a short circuit) between the positive electrode 21 and the negative electrode 22 .
  • the separator 23 includes a polymer compound such as polyethylene.
  • the positive electrode 21 , the negative electrode 22 , and the separator 23 are each impregnated with the electrolytic solution, and the electrolytic solution has the configuration described above. That is, the electrolytic solution includes the electrolyte salt and the lithium fluorophosphate.
  • the positive electrode lead 31 is a positive electrode terminal coupled to the positive electrode current collector 21 A of the positive electrode 21 , and is led from an inside to an outside of the outer package film 10 .
  • the positive electrode lead 31 includes an electrically conductive material such as a metal material. Specific examples of the metal material include aluminum.
  • the positive electrode lead 31 is not particularly limited in shape, and specifically has any of shapes including, without limitation, a thin plate shape and a meshed shape.
  • the negative electrode lead 32 is a negative electrode terminal coupled to the negative electrode current collector 22 A of the negative electrode 22 , and is led from the inside to the outside of the outer package film 10 .
  • the negative electrode lead 32 includes an electrically conductive material such as a metal material. Specific examples of the metal material include copper.
  • the negative electrode lead 32 is led in a direction similar to that in which the positive electrode lead 31 is led. Note that details of a shape of the negative electrode lead 32 are similar to those of the shape of the positive electrode lead 31 .
  • lithium is extracted from the positive electrode 21 , and the extracted lithium is inserted into the negative electrode 22 via the electrolytic solution.
  • lithium is extracted from the negative electrode 22 , and the extracted lithium is inserted into the positive electrode 21 via the electrolytic solution.
  • lithium is inserted and extracted in an ionic state.
  • the positive electrode 21 and the negative electrode 22 are each fabricated, and the secondary battery is assembled using the positive electrode 21 , the negative electrode 22 , and the electrolytic solution, following which stabilization treatment of the secondary battery is performed, according to an example procedure to be described below. Note that the procedure for preparing the electrolytic solution is as described above.
  • a mixture (a positive electrode mixture) in which the positive electrode active material, the positive electrode binder, and the positive electrode conductor are mixed with each other is put into a solvent to thereby prepare a positive electrode mixture slurry in a paste form.
  • the solvent may be an aqueous solvent, or may be an organic solvent.
  • the positive electrode mixture slurry is applied on the two opposed surfaces of the positive electrode current collector 21 A to thereby form the positive electrode active material layers 21 B.
  • the positive electrode active material layers 21 B are compression-molded by means of, for example, a roll pressing machine. In this case, the positive electrode active material layers 21 B may be heated.
  • the positive electrode active material layers 21 B may be compression-molded multiple times. The positive electrode active material layers 21 B are thus formed on the two respective opposed surfaces of the positive electrode current collector 21 A. As a result, the positive electrode 21 is fabricated.
  • the negative electrode 22 is formed by a procedure similar to the fabrication procedure of the positive electrode 21 described above. Specifically, first, a mixture (a negative electrode mixture) in which the negative electrode active material, the negative electrode binder, and the negative electrode conductor are mixed with each other is put into a solvent to thereby prepare a negative electrode mixture slurry in a paste form. Details of the solvent are as described above. Thereafter, the negative electrode mixture slurry is applied on the two opposed surfaces of the negative electrode current collector 22 A to thereby form the negative electrode active material layers 22 B. Lastly, the negative electrode active material layers 22 B are compression-molded. The negative electrode active material layers 22 B are thus formed on the two respective opposed surfaces of the negative electrode current collector 22 A. As a result, the negative electrode 22 is fabricated.
  • a mixture a negative electrode mixture in which the negative electrode active material, the negative electrode binder, and the negative electrode conductor are mixed with each other is put into a solvent to thereby prepare a negative electrode mixture slurry in a paste form. Details of the solvent are as described
  • the positive electrode lead 31 is coupled to the positive electrode current collector 21 A of the positive electrode 21 by a coupling method such as a welding method
  • the negative electrode lead 32 is coupled to the negative electrode current collector 22 A of the negative electrode 22 by a method such as a welding method.
  • the positive electrode 21 and the negative electrode 22 are stacked on each other with the separator 23 interposed therebetween, following which the stack of the positive electrode 21 , the negative electrode 22 , and the separator 23 is wound to thereby fabricate a wound body (not illustrated).
  • the wound body has a configuration similar to that of the battery device 20 except that the positive electrode 21 , the negative electrode 22 , and the separator 23 are each not impregnated with the electrolytic solution.
  • the wound body is pressed by means of, for example, a pressing machine to thereby shape the wound body into an elongated shape.
  • the wound body is placed inside the depression part 10 U, following which the outer package film 10 (the fusion-bonding layer/the metal layer/the surface protective layer) is folded to thereby cause portions of the outer package film 10 to be opposed to each other.
  • outer edge parts of two sides of the fusion-bonding layer opposed to each other are bonded to each other by a bonding method such as a thermal-fusion-bonding method to thereby place the wound body inside the outer package film 10 having the pouch shape.
  • the electrolytic solution is injected into the outer package film 10 having the pouch shape, following which outer edge parts of the remaining one side of the fusion-bonding layer are bonded to each other by a bonding method such as a thermal-fusion-bonding method.
  • the sealing film 41 is interposed between the outer package film 10 and the positive electrode lead 31
  • the sealing film 42 is interposed between the outer package film 10 and the negative electrode lead 32 .
  • the wound body is thereby impregnated with the electrolytic solution, and the battery device 20 that is a wound electrode body is thus fabricated. Accordingly, the battery device 20 is sealed in the outer package film 10 having the pouch shape. As a result, the secondary battery is assembled.
  • the assembled secondary battery is charged and discharged.
  • Various conditions including, for example, an environment temperature, the number of times of charging and discharging (the number of cycles), and charging and discharging conditions may be set as desired.
  • a film is formed on a surface of each of the positive electrode 21 and the negative electrode 22 , which electrochemically stabilizes a state of the secondary battery.
  • the secondary battery is completed.
  • the secondary battery includes an electrolytic solution, and the electrolytic solution has the above-described configuration. It is therefore possible to achieve a superior battery characteristic for the reason described above.
  • the secondary battery may include a lithium-ion secondary battery. This makes it possible to obtain a sufficient battery capacity stably through the use of insertion and extraction of lithium. Accordingly, it is possible to achieve higher effects.
  • the electrolytic solution may include the electrolyte salt including the imide anion and any other electrolyte salt.
  • the electrolytic solution include lithium hexafluorophosphate as the other electrolyte salt, and the content of the electrolyte salt in the electrolytic solution be made appropriate in relation to a content of lithium hexafluorophosphate in the electrolytic solution.
  • the electrolyte salt includes a cation and an imide anion.
  • a hexafluorophosphoric acid ion includes a lithium ion and a hexafluorophosphoric acid ion.
  • a sum T (mol/kg) of a content C1 of the cation in the electrolytic solution and a content C2 of the lithium ion in the electrolytic solution is preferably within a range from 0.7 mol/kg to 2.2 mol/kg both inclusive.
  • a ratio R (mol %) of a mole number M2 of the hexafluorophosphoric acid ion in the electrolytic solution to a mole number M1 of the imide anion in the electrolytic solution is preferably within a range from 13 mol % to 6000 mol % both inclusive.
  • a reason for this is that the migration velocity of the cation and a migration velocity of the lithium ion near the surface of each of the positive electrode and the negative electrode are each sufficiently improved, and the migration velocity of the cation and the migration velocity of the lithium ion are each sufficiently improved also in the electrolytic solution.
  • the “content of the cation in the electrolytic solution” described here is a content of the cation with respect to the solvent
  • the “content of the lithium ion in the electrolytic solution” described here is a content of the lithium ion with respect to the solvent.
  • the secondary battery is disassembled to collect the electrolytic solution, following which the electrolytic solution is analyzed by ICP optical emission spectroscopy.
  • the electrolytic solution is analyzed by ICP optical emission spectroscopy.
  • the electrolytic solution includes the electrolyte salt, and similar effects are therefore obtainable.
  • a total amount (the sum T) thereof is made appropriate, and a mixture ratio (the ratio R) thereof is also made appropriate. Accordingly, the migration velocity of the cation and the migration velocity of the lithium ion near the surface of each of the positive electrode and the negative electrode are each further improved, and the migration velocity of the cation and the migration velocity of the lithium ion are each further improved also in the electrolytic solution. Accordingly, it is possible to achieve higher effects.
  • the separator 23 that is a porous film is used. However, although not specifically illustrated here, a separator of a stacked type including a polymer compound layer may be used.
  • the separator of the stacked type includes a porous film having two opposed surfaces, and the polymer compound layer provided on one of or each of the two opposed surfaces of the porous film.
  • a reason for this is that adherence of the separator to each of the positive electrode 21 and the negative electrode 22 improves to suppress misalignment (winding displacement) of the battery device 20 . This suppresses swelling of the secondary battery even if a side reaction such as the decomposition reaction of the electrolytic solution occurs.
  • the polymer compound layer includes a polymer compound such as polyvinylidene difluoride. A reason for this is that superior physical strength and superior electrochemical stability are obtainable.
  • the porous film, the polymer compound layer, or both may each include one or more kinds of insulating particles.
  • the insulating particles include an inorganic material, a resin material, or both.
  • the inorganic material include aluminum oxide, aluminum nitride, boehmite, silicon oxide, titanium oxide, magnesium oxide, and zirconium oxide.
  • the resin material include acrylic resin and styrene resin.
  • a precursor solution including, without limitation, the polymer compound and a solvent is prepared, following which the precursor solution is applied on one of or each of the two opposed surfaces of the porous film.
  • insulating particles may be added to the precursor solution on an as-needed basis.
  • the separator of the stacked type In the case where the separator of the stacked type is used also, lithium ions are movable between the positive electrode 21 and the negative electrode 22 , and similar effects are therefore obtainable. In this case, in particular, the secondary battery improves in safety, as described above. Accordingly, it is possible to achieve higher effects.
  • the electrolytic solution which is a liquid electrolyte
  • an electrolyte layer which is a gel electrolyte, may be used.
  • the positive electrode 21 and the negative electrode 22 are stacked on each other with the separator 23 and the electrolyte layer interposed therebetween, and the stack of the positive electrode 21 , the negative electrode 22 , the separator 23 , and the electrolyte layer is wound.
  • the electrolyte layer is interposed between the positive electrode 21 and the separator 23 , and between the negative electrode 22 and the separator 23 .
  • the electrolyte layer includes a polymer compound together with the electrolytic solution.
  • the electrolytic solution is held by the polymer compound. A reason for this is that leakage of the electrolytic solution is prevented.
  • the configuration of the electrolytic solution is as described above.
  • the polymer compound includes, for example, polyvinylidene difluoride.
  • a precursor solution including, for example, the electrolytic solution, the polymer compound, and a solvent is prepared, following which the precursor solution is applied on one side or both sides of the positive electrode 21 and on one side or both sides of the negative electrode 22 .
  • lithium ions are movable between the positive electrode 21 and the negative electrode 22 via the electrolyte layer, and similar effects are therefore obtainable.
  • leakage of the electrolytic solution is prevented, as described above. Accordingly, it is possible to achieve higher effects.
  • the secondary battery used as a power source may serve as a main power source or an auxiliary power source of, for example, electronic equipment and an electric vehicle.
  • the main power source is preferentially used regardless of the presence of any other power source.
  • the auxiliary power source is used in place of the main power source, or is switched from the main power source.
  • the applications of the secondary battery include: electronic equipment; apparatuses for data storage; electric power tools; battery packs to be mounted on, for example, electronic equipment; medical electronic equipment; electric vehicles; and electric power storage systems.
  • the electronic equipment include video cameras, digital still cameras, mobile phones, laptop personal computers, headphone stereos, portable radios, and portable information terminals.
  • the apparatuses for data storage include backup power sources and memory cards.
  • the electric power tools include electric drills and electric saws.
  • Examples of the medical electronic equipment include pacemakers and hearing aids.
  • Examples of the electric vehicles include electric automobiles including hybrid automobiles.
  • Examples of the electric power storage systems include home battery systems or industrial battery systems for accumulation of electric power for a situation such as emergency.
  • the above-described applications may each use one secondary battery, or may each use multiple secondary batteries.
  • the battery packs may each include a single battery, or may each include an assembled battery.
  • the electric vehicle is a vehicle that operates (travels) using the secondary battery as a driving power source, and may be a hybrid automobile that is additionally provided with a driving source other than the secondary battery.
  • electric power accumulated in the secondary battery that is an electric power storage source may be utilized for using, for example, home appliances.
  • FIG. 3 illustrates a block configuration of a battery pack.
  • the battery pack described here is a battery pack (a so-called soft pack) including one secondary battery, and is to be mounted on, for example, electronic equipment typified by a smartphone.
  • the battery pack includes an electric power source 51 and a circuit board 52 .
  • the circuit board 52 is coupled to the electric power source 51 , and includes a positive electrode terminal 53 , a negative electrode terminal 54 , and a temperature detection terminal 55 .
  • the electric power source 51 includes one secondary battery.
  • the secondary battery has a positive electrode lead coupled to the positive electrode terminal 53 and a negative electrode lead coupled to the negative electrode terminal 54 .
  • the electric power source 51 is couplable to outside via the positive electrode terminal 53 and the negative electrode terminal 54 , and is thus chargeable and dischargeable.
  • the circuit board 52 includes a controller 56 , a switch 57 , a PTC device 58 , and a temperature detector 59 . However, the PTC device 58 may be omitted.
  • the controller 56 includes, for example, a central processing unit (CPU) and a memory, and controls an overall operation of the battery pack.
  • the controller 56 detects and controls a use state of the electric power source 51 on an as-needed basis.
  • the controller 56 turns off the switch 57 . This prevents a charging current from flowing into a current path of the electric power source 51 .
  • the overcharge detection voltage is not particularly limited, and is specifically 4.20 V ⁇ 0.05 V.
  • the overdischarge detection voltage is not particularly limited, and is specifically 2.40 V ⁇ 0.1 V.
  • the switch 57 includes, for example, a charge control switch, a discharge control switch, a charging diode, and a discharging diode.
  • the switch 57 performs switching between coupling and decoupling between the electric power source 51 and external equipment in accordance with an instruction from the controller 56 .
  • the switch 57 includes, for example, a metal-oxide-semiconductor field-effect transistor (MOSFET).
  • MOSFET metal-oxide-semiconductor field-effect transistor
  • the temperature detector 59 includes a temperature detection device such as a thermistor.
  • the temperature detector 59 measures a temperature of the electric power source 51 using the temperature detection terminal 55 , and outputs a result of the temperature measurement to the controller 56 .
  • the result of the temperature measurement to be obtained by the temperature detector 59 is used, for example, in a case where the controller 56 performs charge/discharge control upon abnormal heat generation or in a case where the controller 56 performs a correction process upon calculating a remaining capacity.
  • Secondary batteries were fabricated, following which the secondary batteries were each evaluated for a battery characteristic as described below.
  • the secondary batteries (lithium-ion secondary batteries) of the laminated-film type illustrated in FIGS. 1 and 2 were fabricated in accordance with the following procedure.
  • the positive electrode active material LiNi 0.82 Co 0.14 Al 0.04 O 2 , which was a lithium-containing compound (an oxide)
  • 3 parts by mass of the positive electrode binder polyvinylidene difluoride
  • 6 parts by mass of the positive electrode conductor carbon black
  • the positive electrode mixture was put into a solvent (N-methyl-2-pyrrolidone, which was an organic solvent), following which the organic solvent was stirred to thereby prepare a positive electrode mixture slurry in a paste form.
  • the positive electrode mixture slurry was applied on the two opposed surfaces of the positive electrode current collector 21 A (a band-shaped aluminum foil having a thickness of 12 ⁇ m) by means of a coating apparatus, following which the applied positive electrode mixture slurry was dried to thereby form the positive electrode active material layers 21 B.
  • the positive electrode active material layers 21 B were compression-molded by means of a roll pressing machine. In this manner, the positive electrode 21 was fabricated.
  • the negative electrode active material artificial graphite, which was the carbon material, having a (002) plane spacing of 0.3358 nm measured by an X-ray diffraction method
  • 7 parts by mass of the negative electrode binder styrene butadiene rubber
  • the negative electrode mixture slurry was applied on the two opposed surfaces of the negative electrode current collector 22 A (a band-shaped copper foil having a thickness of 15 ⁇ m) by means of a coating apparatus, following which the applied negative electrode mixture slurry was dried to thereby form the negative electrode active material layers 22 B.
  • the negative electrode active material layers 22 B were compression-molded by means of a roll pressing machine. In this manner, the negative electrode 22 was fabricated.
  • ethylene carbonate which was the cyclic carbonic acid ester
  • ⁇ -butyrolactone which was a lactone
  • a mixture ratio (a weight ratio) between ethylene carbonate and ⁇ -butyrolactone in the solvent was set to 30:70.
  • a lithium ion (Li + ) was used as the cation of the electrolyte salt.
  • Used as the anion of the electrolyte salt were the respective first imide anions represented by Formulae (1-5), (1-6), (1-21), and (1-22), the second imide anion represented by Formula (2-5), the third imide anion represented by Formula (3-5), and the fourth imide anion represented by Formula (4-37). Contents (mol/kg) of the electrolyte salts were as listed in Table 1.
  • lithium fluorophosphate Used as the lithium fluorophosphate were lithium monofluorophosphate (Li 2 PFO 3 ) and lithium difluorophosphate (LiPF 2 O 2 ). Contents (wt %) of the lithium fluorophosphate were as listed in Table 1.
  • the electrolytic solution including the electrolyte salt and the lithium fluorophosphate was prepared.
  • the electrolyte salt was a lithium salt including an imide anion as the anion.
  • an electrolytic solution for comparison was prepared by a similar procedure, except that a hexafluorophosphoric acid ion (PF 6 ⁇ ) was used as the anion instead of the imide anion, and the lithium fluorophosphate was used.
  • PF 6 ⁇ hexafluorophosphoric acid ion
  • an electrolytic solution for comparison was prepared by a similar procedure, except that the imide anion was used as the anion, and the lithium fluorophosphate was not used.
  • the positive electrode lead 31 (an aluminum foil) was welded to the positive electrode current collector 21 A of the positive electrode 21
  • the negative electrode lead 32 (a copper foil) was welded to the negative electrode current collector 22 A of the negative electrode 22 .
  • the positive electrode 21 and the negative electrode 22 were stacked on each other with the separator 23 (a fine porous polyethylene film having a thickness of 15 ⁇ m) interposed therebetween, following which the stack of the positive electrode 21 , the negative electrode 22 , and the separator 23 was wound to thereby fabricate a wound body. Thereafter, the wound body was pressed by means of a pressing machine, and was thereby shaped into an elongated shape.
  • the separator 23 a fine porous polyethylene film having a thickness of 15 ⁇ m
  • the outer package film 10 (the fusion-bonding layer/the metal layer/the surface protective layer) was folded in such a manner as to sandwich the wound body contained inside the depression part 10 U. Thereafter, the outer edge parts of two sides of the fusion-bonding layer were thermal-fusion-bonded to each other to thereby allow the wound body to be contained inside the outer package film 10 having the pouch shape.
  • an aluminum laminated film was used in which the fusion-bonding layer (a polypropylene film having a thickness of 30 ⁇ m), the metal layer (an aluminum foil having a thickness of 40 ⁇ m), and the surface protective layer (a nylon film having a thickness of 25 ⁇ m) were stacked in this order from an inner side.
  • the electrolytic solution was injected into the outer package film 10 having the pouch shape and thereafter, the outer edge parts of the remaining one side of the fusion-bonding layer were thermal-fusion-bonded to each other in a reduced-pressure environment.
  • the sealing film 41 a polypropylene film having a thickness of 5 ⁇ m
  • the sealing film 42 a polypropylene film having a thickness of 5 ⁇ m
  • the battery device was sealed in the outer package film 10 .
  • the secondary battery was assembled.
  • the secondary battery was charged and discharged for one cycle in an ambient temperature environment (at a temperature of 23° C.). Upon charging, the secondary battery was charged with a constant current of 0.1 C until a voltage reached 4.1 V, and was thereafter charged with a constant voltage of that value, 4.1 V, until a current reached 0.05 C. Upon discharging, the secondary battery was discharged with a constant current of 0.1 C until the voltage reached 2.5 V. Note that 0.1 C was a value of a current that caused a battery capacity (a theoretical capacity) to be completely discharged in 10 hours, and 0.05 C was a value of a current that caused the battery capacity to be completely discharged in 20 hours.
  • a film was thus formed on the surface of each of the positive electrode 21 and the negative electrode 22 , and the state of the secondary battery was therefore electrochemically stabilized. As a result, the secondary battery of the laminated-film type was completed.
  • the electrolytic solution was analyzed by inductively coupled plasma (ICP) optical emission spectroscopy.
  • ICP inductively coupled plasma
  • the secondary batteries were each evaluated for a high-temperature cyclability characteristic, a high-temperature storage characteristic, and a low-temperature load characteristic.
  • the secondary battery was charged and discharged in a high-temperature environment (at a temperature of 60° C.) to thereby measure a discharge capacity (a first-cycle discharge capacity).
  • Charging and discharging conditions were similar to the charging and discharging conditions for the stabilization of the secondary battery described above.
  • the secondary battery was repeatedly charged and discharged in the same environment until the total number of cycles reached 100 to thereby measure the discharge capacity (a 100th-cycle discharge capacity).
  • Charging and discharging conditions were similar to the charging and discharging conditions for the stabilization of the secondary battery described above.
  • cyclability retention rate (%) (100th-cycle discharge capacity/first-cycle discharge capacity) ⁇ 100.
  • the secondary battery was charged and discharged for one cycle in an ambient temperature environment (at a temperature of 23° C.) to thereby measure a discharge capacity (a pre-storage discharge capacity).
  • Charging and discharging conditions were similar to the charging and discharging conditions for the stabilization of the secondary battery described above.
  • the secondary battery was charged and discharged for one cycle in an ambient temperature environment (at a temperature of 23° C.) to thereby measure a discharge capacity (a first-cycle discharge capacity).
  • Charging and discharging conditions were similar to the charging and discharging conditions for the stabilization of the secondary battery described above.
  • the secondary battery was repeatedly charged and discharged in a low-temperature environment (at a temperature of ⁇ 10° C.) until the total number of cycles reached 100 to thereby measure the discharge capacity (a 100th-cycle discharge capacity).
  • Charging and discharging conditions were similar to the charging and discharging conditions for the stabilization of the secondary battery described above, except that the current at the time of discharging was changed to 1 C. Note that 1 C was a value of a current that caused a battery capacity to be completely discharged in 1 hour.
  • load retention rate (%) (100th-cycle discharge capacity/first-cycle discharge capacity) ⁇ 100.
  • each of the cyclability retention rate, the storage retention rate, and the load retention rate varied greatly depending on the configuration of the electrolytic solution.
  • each of the cyclability retention rate, the storage retention rate, and the load retention rate decreased.
  • each of the cyclability retention rate and the load retention rate increased, or only the cyclability retention rate increased, as compared with the case where the electrolytic solution included neither the imide anion nor the lithium fluorophosphate (Comparative example 1).
  • each of the cyclability retention rate, the storage retention rate, and the load retention rate increased, but each of the cyclability retention rate, the storage retention rate, and the load retention rate did not increased sufficiently, as compared with the case where the electrolytic solution included neither the imide anion nor the lithium fluorophosphate (Comparative example 1).
  • secondary batteries were fabricated by a procedure similar to that in Example 3, except that one of the additive or the other electrolyte salt was added to the electrolytic solution, following which the secondary batteries were each evaluated for a battery characteristic.
  • VC vinylene carbonate
  • VEC vinylethylene carbonate
  • MEC methylene ethylene carbonate
  • FEC monofluoroethylene carbonate
  • DFEC difluoroethylene carbonate
  • PS propane sultone
  • PRS propene sultone
  • CD cyclodysone
  • SA Succinic anhydride
  • PSAH Propanedisulfonic anhydride
  • DTD Ethylene sulfate
  • Succinonitrile SN
  • HMI Hexamethylene diisocyanate
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiFSI lithium bis(fluorosulfonyl)imide
  • LiBOB lithium bis(oxalato)borate
  • the content (wt %) of each of the additive and the other electrolyte salt in the electrolytic solution were as listed in Tables 2 and 3.
  • the electrolytic solution was analyzed by ICP optical emission spectroscopy. As a result, it was confirmed that the kind and content of the additive and the kind and content of the other electrolyte salt were as listed in Tables 2 and 3.
  • secondary batteries were fabricated by a procedure similar to that in Example 3, except that the electrolytic solution included the other electrolyte salt (lithium hexafluorophosphate (LiPF 6 )), following which the secondary batteries were each evaluated for a battery characteristic.
  • the electrolytic solution included the other electrolyte salt (lithium hexafluorophosphate (LiPF 6 )), following which the secondary batteries were each evaluated for a battery characteristic.
  • the other electrolyte salt was added together with the electrolyte salt to the solvent, following which the solvent was stirred.
  • the content (mol/kg) of the electrolyte salt, the content (mol/kg) of the other electrolyte salt, the sum T (mol/kg), and the ratio R (mol %) were as listed in Tables 4 and 5.
  • the electrolytic solution included the electrolyte salt and the lithium fluorophosphate
  • the electrolyte salt included, as the imide anion, one or more of the respective anions represented by Formulae (1) to (4)
  • the lithium fluorophosphate included lithium monofluorophosphate, lithium difluorophosphate, or both
  • each of the cyclability retention rate, the storage retention rate, and the load retention rate was improved.
  • the secondary battery therefore achieved a superior high-temperature cyclability characteristic, a superior high-temperature storage characteristic, and a superior low-temperature load characteristic. Accordingly, it was possible to achieve a superior battery characteristic.
  • the device structure of the battery device is not particularly limited.
  • the device structure may be, for example, a stacked type or a zigzag folded type.
  • the positive electrode and the negative electrode are stacked on each other with the separator interposed therebetween.
  • the zigzag folded type the positive electrode and the negative electrode are opposed to each other with the separator interposed therebetween, and are folded in a zigzag manner.
  • the electrode reactant is lithium
  • the electrode reactant is not particularly limited.
  • the electrode reactant may be another alkali metal such as sodium or potassium, or may be an alkaline earth metal such as beryllium, magnesium, or calcium, as described above.
  • the electrode reactant may be another light metal such as aluminum.

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